New dye for wool of the safranine series



I Patented 'Dec. 9, 1924.

.7QUNITEDQSTATES PATENT OFFICE. f

WILH ELM HEBZBERG, OI IBERLIN-WILMEBSDOBF, AND OSWALD SCHARFENBEBG, OF

BERLIN -SGH ONE'.BERG, GERMANY, ASSIGNORS TD ACTIEN GESELLSCEAFT F'U'l ANILIN FABRIKATION, OI BERLIN, GERMANY.

NEW DYE WOOL OF THE SAFRANINE SERIES.

No Drawing.

To all whom it may concern:

Be it known that we, WILHELM HERZBERG and OSWALD SCHARFENBERG, citizens of the German Republic, residing at Berlin-Wilmersdorf, Germany, and Berlin-Schoneberg,

Germany, have invented certain new and useful Improvements in New Dyes for- Wool of the Safranine'Series, of which the following is a specification.

the safranine series consisting in treating an iso-rosinduline in the presence of oxygen or an oxidizing agent with ammonia or with a primary amine is well-known (see German specifications Nos. 97118, 97 365, a 97 395,

97396 and 102362).

In the German specification No. 97396 it is stated that substituted iso-rosindulines, for example suphonic a'cids, maybensed. 2 According to the present invention, ifin Y the benzene nucleus the hydrogen atom ad-' manner, for example by the condensation of a tertiary aromatic amine containing in the 4-position an aminoand in the 3-position a i sulphonic group, with a 2-arylam1nonaphthalene, with a derivative thereof etc.

The following examples illustrate the invention, the parts beingiby weight: v

Ewample 1.Into a solution heated to 40 8590 G. made from 400 parts of water, 30

parts of 3-sulphophenyl-2-naphthylamine (which may beobtained. by boiling a mixture of 2-oxynaphthlene and l-aminobenzene-3-sulphonic acid with sodium bisulphite lye) and 22 parts of l-dimethylaminoeaminobenzene-3-sulphonic acid (obtained by- A method of manufacturing dyest'ufis 0f- Application filed November-20, 1923. Serial No. 675,920. I

reducing the dyestufi derived from any. diazo-compound and 1-dimethylamino-3- sulphonic acid) there is allowed to run a solution of 30 parts of sodium bichromate in-60parts of water, .125 parts of acetic f acid ,of 30 per cent strength being added. The iso-rosindulinedisulphonic acid thus obtained crystallizes partly after cooling. It dissolves in concentrated sulphuric acid to a reddish violet solution. v

For the manufacture of the safranine it is not necessary to separate the intermediate product. After oxidation the solution is allowed to run into a solution of 19 parts of 1.4-diaminobenzene-Q-sulphonic acid in 200 I parts of water, 90 parts of sodium hydroxide solution of 40 Baum specific gravity and 50 parts of crystallized sodium sul hite being added. A current of air is in own through the solution, until a sample of the isolated safranine dissolves to a clear green solution in concentrated sulphuric acid. By addition of 20 parts off-sodium bicarbonate the excess of, sodium hydroxide is neutralized; the solution is then filtered from the chromium hydroxide which has separated. From the filtrate the safranine is precipitated by addition of common salt. It dyes wool clear blue tints.

' Many variations may be made in theex- ,ample without departing from the scope of phophenyl-2-naphthylamine manufactured' in the described manner starting from 2- oxynaphthalene and 1-aminophenyl-4-su1- phonic acid; other derivatives of phenyl-2- napthylamine containing another substituent, such as halogen, may be employed. Instead of1-dimethylamino-4-aminobenzene-3- sulphonic acid another suitable sulphonic acid of a tertiary para-diamine may be used, for instance the corresponding diethyl compound, -a'mino-ethyl-l-sulphobenzylaniline-3-sulphonic acid etc. v

I Furthermore for the lA-diaminobenzene 2-sulphonic acid'servlng in the example as stituted another suitable sulphonic acid of an aromatic para-diamine, a non-sulpho 1 phenylaminonaphthale'ne-6-sulphonic tion. more reddish by addition of sodium carbonate and reddish violet by addition of so-, to the gener a1 formula;

nated aromaticpara-diamine etc.

Example I phonic acid prepared from 30 parts of aci and 24.5 parts of I-diethyl-15-amino-4aminobenzene-3-sulphonic acid is converted into the safraninedi'sulphonic acid b treating with 30 parts of 1-para-toluenesu phamino- 4-amino-2-chlorobenzene and an oxidizing agent and by eliminating the acidyl group.

The dyestufi' thus obtained dyes wool in an acid bath greenish blue tints; it forms in the state of its sodium salt'a dark powder showing metallic lustre, dissolving in concentrated sulphuric acid to a'greenis'h solu- The blue aqueous solution becomes dium hydroxide solution.

Ewample 3:43 parts of the iso-rosinduline sul honic acid (described in Example 5 of the german specification N 0. 97396) are converted with'aid of 30 parts of 1-paratoluenesulphamino-4-amino-2-chlorobenzene 'by the oxidizing process described in Example 1 into the corresponding safranine'.

lo-sulphonate the safraninemonosulphonic acid and to eliminate the acid 1 group it is heated to 50-60 C. with phuric acid containing 25 per cent of anhydride until a sample separated by water dissolves in a solution of sodium carbonate, The dyestufi' isfinished in the'us'ual manner. It. shows as well as the dyestufl described in Example 1 the like the dyestuff of Example 2. v

For the parent materials used "in Examples 2 and 3 others may be substituted in the same manner as described in Example 1.

.Finally as to the several steps of the process according to the invention for the two oxidation processes (forming the iso-rosinproperties of duline sulphonic acid and then the safra- Y 7 nine) any other suitable oxidizing process than that given in the examples may be used.

Having now described our invention what we claim 1s.

1. The herein-described new dyes for W001 of'the safranine series, being in the state 01' their sodium salts dark powders with a metallic lustre, dissolving in concentrated sulphuric acid to greenish solutions and in water to blue solutions which become more reddish by addition of sodium carbonate and reddish violet by addition of sodium hydroxide solution, dyeing on' wool in an acid bath blue tints, containing at least two sulphonic acid groups and derived from 2.4118 iso-rosin'dulinedisuL- uming sulof the benzene series.

2. The herein-described new 'dyes' f or wool.

of the safranine series being inthe state of their sodium salts dark powders with a rhetallicdustre, dissolving in concentrated sulphuric acid to greenish solutions and in water to blue solutionswhich-become more reddish by addition of sodium carbonate and reddish violet by addition of sodium vhydroxide solution dyeing onwool in an acid bath blue tints containing at least two sulphonic acid groups and derlvedflfrom the safranlnes which correspondas free acids safranines which correspond as free acids to the general formula:

their sodium salts dark powders with a metallic lustre, dissolving in concentrated sulphuric acid. to greenish solutions and in water to blue solutions which become more reddish by addition of sodium carbonate and p, g, X, Y meaning univalent radicals. V 4

reddish violet by addition of sodium by phuric acid to greenish solutions and in sulphonic groups and derived from the reddish by addition of sodium carbonate droxide solution, dyeing on wool m an acid and reddish violet by addition of sodium bath blue tints containing at least two-sul hydroxide solution, dyeing onwool in an phonic roups and derived-from the. safraacid bath blue tints containing two sul-, nines w ich correspond as free-acids to the phonic roups and derived from the safraeneral formula: nines w ich corres 0nd as free acidsto the l g P general formula: 5

* sour I n; Y is N I 0.11 v N not Nflz /L/ 9 NH l soin 5. The herein-described new dyes for wool of the safranine series being in the state of their sodium salts dark powders with a metallic lustre, dissolving in concentrated sulg, X, Y meaning univalent radicals.

7. The herein-described new dye for wool of the safranine series being in the state of its sodium salt a dark powder with a metfaflic lustre, dissolving in concentrated sulphuric acid to a greenish solution and in water to a blue solution which becomes more reddish by addition of sodium carbonate and reddish violet by addition of sodium hydroxidesolution, dyeing on wool in an acid bath blue tints and corresponding as free acid to the general formula:

water to blue solutions which become more reddish by"addition of sodium carbonate and reddish violet by addition of sodium hydroxide solution, dyeing on wool in .an acid bath blue tints, containing at least two safranines which correspond as free acids to the general formula:

' "l l Nib Y SOH X, Y meaning univalent radicals.

6. The herein-described new dyes for woof N N N CIH| NH Cl 03H In testimony whereof we afiix our/signatures n presence of two witnesses.

WILHELM HERZBERG. of the salframne series being 111 the state of I v their sodium salts dark powders with a me- .OSWALD SCHARFENBERG' tallic lustre, dissolving in concentrated sul- Witnesses: phuric acid to greenish solutions and in E. KLIIPBEL,

water to blue solutions which become more E. HOLTZ ERMON. 

